• Title/Summary/Keyword: first-order reaction

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Kinetic Study on Bromine-Exchange Reaction of Antimony Tribromide with t-Butyl Bromide in Nitrobenzene and in 1, 2, 4-Trichlorobenzene$^*$

  • Choi, Sang-Up;Pae, Young-Il
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.144-148
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    • 1982
  • The kinetic study on the bromine-exchange reaction of antimony tribromide with t-butyl bromide in nitrobenzene or 1,2,4-trichlorobenzene has been carried out, using Br-82 labelled antimony tribromide. The results show that the exchange reaction is first order with respect to t-butyl bromide and 1.5th order with respect to antimony tribromide. It is assumed that the 1.5th order indicates the coexistance of first- and second-order kinetics. Reaction mechanisms for the exchange reaction are proposed.

Modeling and Application of Chlorine Bulk Decay in Drinking Water Distribution System (배급수계통에서 잔류염소 감소 특성 및 적용연구)

  • Ahn, Jae-Chan;Park, Chang-Min;Koo, Ja-Yong
    • Journal of Korean Society of Water and Wastewater
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    • v.19 no.4
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    • pp.487-496
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    • 2005
  • Chlorine bulk decay tests were carried out by bottle test under controlled conditions in a laboratory. Experiments were performed at different temperatures: $5^{\circ}C$, $15^{\circ}C$, $25^{\circ}C$, and the water temperatures when samples were taken from the effluent just before entering to its distribution system. 38 bulk tests were performed for water of Al (water treatment plant), 4 bulk tests for A2 (large service reservoir), and A3(pumping station). Residual chlorine concentrations in the amber bottles were measured over time till about 100 hours and bulk decay coefficients were evaluated by assuming first-order, parallel first-order, second-order. and $n^{th}-order$ reaction. The $n^{th}-order$ coefficients were obtained using Fourth-order Runge-Kutta Method. A good-fit by the average coefficient of determination ($R^2$) was first-order ($R^2=0.90$) < parallel first-order ($R^2{_{fast}}=0.92$, $R^2{_{slow}}=0.95$) < second-order ($R^2=0.95$) < $n^{th}-order$ ($R^2=0.99$). But if fast reaction of parallel first-order bulk decay were applied to the effluent of large service reservoir with ca. 20 hours of travel time and slow reaction in the water distribution system following the first 20 hours, parallel first-order bulk decay would be best and easy for application of water quality modeling technique.

Bromine-Exchange Reaction of Antimony Tribromide with Benzyl Bromide in Nitrobenzene and in 1,2,4-Trichlorobenzene$^*$

  • Choi Sang Up;Pae Young Il;Rhyu Sok Hwan
    • Bulletin of the Korean Chemical Society
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    • v.3 no.2
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    • pp.55-60
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    • 1982
  • The rate of the bromine-exchange reaction of antimony tribromide with benzyl bromide in nitrobenzene or 1,2,4-trichlorobenzene has been measured, using Br-82 labelled antimony tribromide. The result of the study indicates that the exchange reaction is first order with respect to benzyl bromide, and either second or first order with respect to antimony tribromide depending on its concentrations. The second-order kinetics with respect to antimony tribromide have been observed at relatively high $[SbBr_3]$ concentrations, and the first-order kinetics at lower $[SbBr_3]$ concentrations. Reaction mechanisms are proposed for the exchange reaction.

Reduction of Alkyl Halides by Homonuclear Bridging Hydride, (μ-H)[(η$^5-MeCp)$Mn(CO)₂]₂-ppn+

  • 박용광;김영웅
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.269-273
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    • 1996
  • Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

Kinetic Study on Bromine-Exchange Reaction of Antimony Tribromide with $\alpha$-Phenylethyl Bromide in Nitrobenzene

  • Choi, Sang-Up;Pae, Young-Il;Rhyu, Sok-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.6 no.3
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    • pp.124-127
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    • 1985
  • The kinetic study on the bromine-exchange reaction of antimony tribromide with ${\alpha}$-phenylethyl bromide in nitrobenzene has been carried out, using Br-82 labelled antimony tribromide. The results show that the exchange reaction is first order with respect to ${\alpha}$-phenylethyl bromide, and either second or first order with respect to antimony tribromide depending on its concentration. It is also concluded that ${\alpha}$-phenylethyl bromide exchanges bromine atom with antimony tribromide much faster than other organic bromides previously examined. Reaction mechanisms for the exchange reaction are discussed.

The Effect of $H^+$ on Reduction of $[Co(NH_3)_4(C_2O_4)]^+$ with $[Fe(H_2O)_6]^{2+}$

  • Lim, Joo-Sang;Lee, Jae-Weon;Kang, Seung-Gu;Park, Byung-Kak
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.303-306
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    • 1990
  • Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

Kinetics of Reversible Consecutive Reactions

  • Park, Tae Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.243-245
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    • 2013
  • Rate equations are exactly solved for the reversible consecutive reaction of the first-order and the time-dependence of concentrations is analytically determined for species in the reaction. With the assumption of pseudo first-order reaction, the calculation applies and determines the concentration of product accurately and explicitly as a function of time in the unimolecular decomposition of Lindemann and in the enzyme catalysis of Michaelis-Menten whose rate laws have been approximated in terms of reactant concentrations by the steady-state approximation.

Quantitative Evaluation of the First Order Creatine-Kinase Reaction Rate Constant in in vivo Shunted Ovine Heart Treated with Oxandrolone Using Magnetization Transfer 31P Magnetic Resonance Spectroscopy (MT-31P-MRS) and 1 H/31P Double-Tuned Surface Coil: a Preliminary Study

  • Thapa, Bijaya;Dahl, Marjanna;Kholmovski, Eugene;Burch, Phillip;Frank, Deborah;Jeong, Eun-Kee
    • Investigative Magnetic Resonance Imaging
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    • v.22 no.1
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    • pp.26-36
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    • 2018
  • Purpose: Children born with single ventricle physiology demonstrate poor growth rate and suffer from malnutrition, which lead to increased morbidity and mortality in this population. We assume that an anabolic steroid, oxandrolone, will promote growth in these infants by improving myocardial energy utilization. The purpose of this paper is to study the efficacy of oxandrolone on myocardial energy consumption in these infants. Materials and Methods: We modeled single ventricle physiology in a lamb by prenatally shunting the aorta to the pulmonary artery and then postnatally, we monitored cardiac energy utilization by quantitatively measuring the first order reaction rate constant, $k_f$ of the creatine-kinase reaction in the heart using magnetization transfer $^{31}P$ magnetic resonance spectroscopy, home built $^1H/^{31}P$ transmit/receive double tuned coil, and transmit/receive switch. We also performed cine MRI to study the structure and dynamic function of the myocardium and the left ventricular chamber. The spectroscopy data were processed using home-developed python software, while cine data were analyzed using Argus software. Results: We quantitatively measured both the first order reaction rate constant and ejection fraction in the control, shunted, and the oxandrolone-treated lambs. Both $k_f$ and ejection fraction were found to be more significantly reduced in the shunted lambs compared to the control lambs, and they are increased in oxandrolone-treated lambs. Conclusion: Some improvement was observed in both the first order reaction rate constant and ejection fraction for the lamb treated with oxandrolone in our preliminary study.

A Study on the Transesterification Reaction between Methyl Methacrylate and Diethanolamine (II) (메틸메타크릴레이트와 디에탄올아민과의 에스테르 교환반응에 관한 연구(II))

  • Sohn, Byoung-Chung;Park, Keun-Ho;Jeong, Soon-Wook
    • Journal of the Korean Applied Science and Technology
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    • v.4 no.1
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    • pp.67-71
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    • 1987
  • The transesterification reaction between diethanolamine and methyl methacrylate was kinetically investigated in the presence of various metal acetate catalysts at $120^{\circ}C$. The amount of reacted methyl methacrylate was measured by gas chromatography and liquid chromatography, and the reaction rate also measured from the amount of reaction products and reactants under each catalyst. The transesterification reaction was carried out in the first order with respect to the concentration of diethanolamine and methyl methacrylate, respectively. The over-all order is 2nd. The apparent rate constant was found to obey first-order kinetics with respect to the concentration of catalyst. The maximum reaction rate was appeared at the range of 1.4 to 1.6 of electronegativity of metal ions and instability constant of metal acetates.

A Study on the Catalytic Activity of Nontoxic Organometallic Compound in Esterification Reaction between Succinic Acid and 1,4-Butanediol (Succinic Acid과 1,4-butanediol의 에스테르화반응에서 무독성 유기금속 화합물의 촉매 활성에 관한 연구)

  • Park, Keun-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.27 no.1
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    • pp.6-13
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    • 2010
  • Esterification reaction between succinic acid and 1,4-butanediol was kinetically investigated in the presence of nontoxic organometallic compound catalyst(ESCAT-100E) at $150-190^{\circ}C$. The reaction rates measured by the amount of distilled water from the reaction vessel. The Esterification reaction was carried out under the first order conditions respect to the concentration of reactants, respectively. The overall reaction order was 2nd. The linear relationship was shown between apparent reaction rate constant and reciprocal absolute temperature. By the Arrhenius plot the activation energy have been calculated as 376.13 kJ/mol under nontoxic organometallic compound catalyst and also apparent reaction rate constant, k' was found to obey first kinetics with respect to the concentration of catalyst.